US3760011A - Triols by hydrogenation of bicyclic furodioxoles - Google Patents
Triols by hydrogenation of bicyclic furodioxoles Download PDFInfo
- Publication number
- US3760011A US3760011A US00816073A US3760011DA US3760011A US 3760011 A US3760011 A US 3760011A US 00816073 A US00816073 A US 00816073A US 3760011D A US3760011D A US 3760011DA US 3760011 A US3760011 A US 3760011A
- Authority
- US
- United States
- Prior art keywords
- process according
- range
- psi
- hydrogenation
- furodioxole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H9/00—Compounds containing a hetero ring sharing at least two hetero atoms with a saccharide radical
- C07H9/02—Compounds containing a hetero ring sharing at least two hetero atoms with a saccharide radical the hetero ring containing only oxygen as ring hetero atoms
- C07H9/04—Cyclic acetals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/22—Trihydroxylic alcohols, e.g. glycerol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
- C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
- C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
Definitions
- This invention relates to novel polyhydroxy compounds and to their preparation. More particularly, the invention is concerned with novel organic triols having the neopentyl structure and to methods for their preparation.
- the novel triols of the present invention can be regarded generically as 3,3-dialkyI-l,2,4-butanetriols.
- the invention compounds have the formula HO-CHa-JJ-CH-CHr-OH wherein R and R are the same or different and each of R and R are alkyl groups of one to carbon atoms, preferably one to four carbon atoms.
- the invention compounds are useful solvents and humectants as well as intermediates in the preparation of alkyd resins and plasticizers for resinous materials such as polyvinyl chloride compositions.
- the instant novel 3,3-dialkyl-l,2,4-butanetriols can be prepared according to the method of this invention by the catalytic hydrogenation of certain bicyclic furodioxoles.
- the method of preparing the invention compounds comprises the catalytic hydrogenation, preferably in the presence of water, of certain bicyclic furodioxoles, hereinafter more fully described, at temperatures in the range of 75C. to 175C. at pressures ranging from about 100 to 10,000 psi.
- the bicyclic furodioxole is preheated to the hydrogenation temperature under a hydrogen atmosphere at a pressure below the actual hydrogenation pressure. Following this preheat, the pressure is elevated to the desired level at which the reduction is effected.
- the product triol can be recovered by any suitable means from the crude hydrogenation effluent.
- Bicyclic furodioxole compounds suitable for use in the preparation of the novel polyhydroxy compounds of this invention include tetrahydro-2-alkyl-6,6- dialkylfuro-[2,3-d]-l ,3-dioxoI-5-ols of the formula:
- R and R are the same or different and each of R and R are alkyl groups of one to 10 carbon atoms, preferably one to four carbon atoms.
- the aqueous bases which are most effective in the condensation include the alkali metal carbonates and acetates such as sodium carbonate, potassium carbonate and sodium acetate.
- a preferred bicyclic furodioxole is tetrahydro- 2-isopropyl-6,6-dimethylfuro-[2,3-d1-l ,3-dioxol-5-0l, which is formed from the condensation of isobutyraldehyde and glyoxal.
- Tetrahydro-2-isopropyl-6,6- dimethyIfuro-[2,3-d]-l,3-dioxol-5-ol is hydrogenated according to the method of our invention to yield 3,3- dimethyl-l,2,4-butanetriol as a particularly preferred embodiment of our invention.
- bicyclic furodioxole compound has three carbon-oxygen bonds which must be rather specifically broken in order to obtain the desired product:
- HO-CH Generally, the hydrogenolysis of aliphatic carbonoxygen ether bonds is a reaction ordinarily requiring elevated temperatures. For example, it has been reported that dialkyl ethers are stable to hydrogen at temperatures less than 250C. over nickel, [Adkins, Reaction of Hydrogen with Organic Compounds over Copper-Chromium Oxide and Nickel Catalysts, University of Wisconsin Press (1937) p. 73]. It has also been reported that the reduction of tetrahydrofurfuryl alcohol to 1,5-pentanediol was carried out at 255C. over copper chromite, [Kaufman et al., Organic Synthesis, 26 83 1946)].
- bicyclic furodioxole compounds are susceptible to thermal decomposition, forming hydroxyfuranones:
- hydroxyfuranones are more stable to hydrogenation and the formation of these compounds by thermal decomposition deleteriously affects the yield of desired triol.
- bicyclic furodioxoles can be converted to 3,3-dialkyl-l,2,4-butanetriols at high conversions and yields with little, if any, thermal decomposition of bicyclic furodioxole to hydroxyfuranone compounds and the substantial elimination of hydrogenolysis or chain scission of the trio].
- the desired conversion is accomplished by the catalytic hydrogenation, preferably in the presence of water, of the starting bicyclic furodioxole at moderate temperatures and superatmospheric pressures.
- bicyclic furodioxole compounds are catalytically hydrogenated at a temperature in the range of about 75C.
- the hydrogenation is effected at pressures ranging from about 100 psi to about 10,000 psi, preferably about 100 psi to about 6,000 psi, with excellent results being obtained at pressures in the range of 2,000-5,000 psi. It has also been found beneficial to preheat or soak the starting material in the presence of the catalyst for from about 30 minutes to about 4 hours under a hydrogen atmosphere at a pressure below the actual hydrogenation pressure,v for example, from about 100 to about 1,500 psi.
- the pressure is raised to the desired level, say on the order of 2,000 to 6,000 psi, at which reduction is effected.
- the starting material isplaced in contact with the catalyst under a hydrogen atmosphere at a pressure in the range of about 100 psi to about 1,500 psi, more particularly, 1,000 to 1,500 psi.
- the temperature is raised to the hydrogenation temperature, e.g., 75C. to 175C., and the pressure is then raised to the desired level, e.g., 2,000-6,000 psi, at which reduction is effected.
- the catalysts useful in the process of our invention include the hydrogenation catalysts, e.g., metals of Groups V-B, VI-B, VII-B and VIII of the periodic system and compounds thereof.
- Conventional mixed hydrogenation catalysts such as copper-chromium oxide catalysts, may also be used.
- Representative catalysts include rhdoium, ruthenium, rhenium, osmium, iridium, palladium, platinum, copper-chromium oxide (copper chromite), iron, copper, nickel and cobalt.
- the metals may be used in the form of Raney catalysts.
- the catalysts can be used in finely divided or pelleted form as such or can be supported on an inert carrier such as silica, alumina, silica gel, pumice, kielseguhr, etc.
- Preferred catalysts include Raney nickel, cobalt, palladium on alumina, and copper chromite.
- concentration of the catalyst is not critical and will generally be in the range of about 0.5 to about 20 weight percent, preferably 0.5 to 12 weight percent, based on furodioxole charge.
- the presence of water is advantageous in achieving maximum catalytic efficiency. With water present, catalyst concentrations as low as 0.5 to 2.0 weight percent, based on furodioxole charged, can be used to obtain the product trio] in high conversions and yields.
- concentration of water is not critical and can be varied from 20 to percent of the furodioxole charged. Higher concentrations of water may be used although there appears to be no advantage in doing so. If desired, the use of water can be completely eliminated by using a sufficiently high catalyst concentration, e.g., 10 percent, based on the furodioxole charged.
- a solution of 450 g. of potassium carbonate dissolved in 450 g. of water is added incrementally to a stirred mixture consisting of 6,000 ml. ofwater, 1800 g. of isobutyraldehyde and 1,800 g. of glyoxal.
- the time required for addition is 2 hours.
- the reaction temperature increases from 24C. to 42C.
- the mixture is stirred for 4 additional hours.
- An organic layer is separated from to reaction mixture.
- the crude product is washed once with an equal volume of water and then is heated to 50C. at reduced pressures to remove water and unreacted aldehydes.
- the resulting base product solidifies to give a white waxy solid.
- Tetrahydro-2-isopropy1-6,6- dimethylfuro-[2,3-d]-l,3-dioxol'5-ol (2,020 g.) is obtained.
- a process for the preparation of a compound having the formula wherein R and R are the same or different and each of R and R is an alkyl group having from one to 10 carbon atoms which comprises contacting a bicyclic furodioxole having the formula d 3.
- said hydrogenation catalyst is selected from the class consisting of palladium, platinum, ruthenium, rhenium, rhodium, nickel, cobalt, iron, copper-chromite or mixtures thereof.
- said bydrogenation catalyst is selected from the group consisting of palladium, platinum, ruthenium, rhenium, rhodium, nickel, cobalt, iron, copper chromite or mixtures thereof.
- a process according to claim 10 wherein said hydrogenation catalyst is Raney nickel.
- a process according to claim 12 wherein said catalyst is selected from the class consisting of palladium, platinum, ruthenium, rhenium, rhodium, nickel, cobalt, iron, copper chromite or mixtures thereof.
- a process according to claim 13 wherein said preheating is effected under a hydrogen pressure in the range of 1,000 to 1,500 psi.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US79880369A | 1969-02-12 | 1969-02-12 | |
US81607369A | 1969-04-14 | 1969-04-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3760011A true US3760011A (en) | 1973-09-18 |
Family
ID=27122036
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00816073A Expired - Lifetime US3760011A (en) | 1969-02-12 | 1969-04-14 | Triols by hydrogenation of bicyclic furodioxoles |
Country Status (3)
Country | Link |
---|---|
US (1) | US3760011A (fi) |
FR (1) | FR2035337A5 (fi) |
GB (1) | GB1295696A (fi) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4475004A (en) * | 1983-12-21 | 1984-10-02 | Ethyl Corporation | Preparation of alkanediols |
US4476332A (en) * | 1983-12-21 | 1984-10-09 | Ethyl Corporation | Preparation of alkanediols |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2174651A (en) * | 1937-05-17 | 1939-10-03 | Hercules Powder Co Ltd | Hydrogenation process |
US2440929A (en) * | 1945-05-25 | 1948-05-04 | Ici Ltd | Production of 1:5-pentanediol |
CA527170A (en) * | 1956-07-03 | N. Lacey Richard | Hydrogenation process | |
US2898492A (en) * | 1955-12-13 | 1959-08-04 | Gen Electric | Apparatus for and method of cooling beam transmitting windows |
US3168534A (en) * | 1961-12-28 | 1965-02-02 | Shell Oil Co | Hydroxylation products of dihydropyran derivatives and their hydrogenation to tetrahydroxy alkanes |
-
1969
- 1969-04-14 US US00816073A patent/US3760011A/en not_active Expired - Lifetime
-
1970
- 1970-02-12 FR FR7004964A patent/FR2035337A5/fr not_active Expired
- 1970-02-12 GB GB1295696D patent/GB1295696A/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA527170A (en) * | 1956-07-03 | N. Lacey Richard | Hydrogenation process | |
US2174651A (en) * | 1937-05-17 | 1939-10-03 | Hercules Powder Co Ltd | Hydrogenation process |
US2440929A (en) * | 1945-05-25 | 1948-05-04 | Ici Ltd | Production of 1:5-pentanediol |
US2898492A (en) * | 1955-12-13 | 1959-08-04 | Gen Electric | Apparatus for and method of cooling beam transmitting windows |
US3168534A (en) * | 1961-12-28 | 1965-02-02 | Shell Oil Co | Hydroxylation products of dihydropyran derivatives and their hydrogenation to tetrahydroxy alkanes |
Non-Patent Citations (1)
Title |
---|
Broquet et al., Chem. Abstracts , Vol. 67, (1967), page 7,724, item 82010Y. * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4475004A (en) * | 1983-12-21 | 1984-10-02 | Ethyl Corporation | Preparation of alkanediols |
US4476332A (en) * | 1983-12-21 | 1984-10-09 | Ethyl Corporation | Preparation of alkanediols |
Also Published As
Publication number | Publication date |
---|---|
GB1295696A (fi) | 1972-11-08 |
FR2035337A5 (fi) | 1970-12-18 |
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